Fungicidal and insecticidal preparations



."fungicides and insecticides.

Patented Oct. 28, 1952 FUNGICIDAL AND INSECTICIDAL PREPARATIONS I Albert J. S-hmi'dl, Greens Bayou, Tex., assignor,

by mcsne assignments, to Standard Oil Developmentv Company, Elizabeth, N.-J., a corporation of Delaware 'No Drawing. Application January 3, 1950, Serial No. 136,643

'I'h e present invention is directed to an improved insecticide and fungicide. More particularly, the invention is directed to a fungicide and insecticide which contains a halogen.

Prior to the present invention it has been 1 known to employ halogenated hydrocarbons as Typical of the prior art is Reissue 22,597 to Ladd, 2,286,222 to Moyle and Fletcher and 2,362,563 and 2,362,565- also to Ladd. These patents teach various chlorinated hydrocarbon derivatives as insecticides and para- -siticides and have the common property of the *carbonatoms in the ring being halogenated.

While halogenation of the carbon atoms in the "ring increases the toxicity to insects and para- -sites and fungi, it also increases the toxicity to higher animal life such as the vertebrate and mammalian forms.

It is therefore the main object of the present invention to provide an improved insecticide and fungicide which may be safely used in contact with higher animal life.

Another object of the present invention is to provide a novel and useful halogenated hydrocarbon adapted to be used as an insecticide and I the compound such that it is on the non-aromatic carbon atoms in the compound.

In accordance with the present invention an improved insecticide and fungicide is provided comprising a halogenated duroquinone contain.- ing an average. of more than by weight of halogen substituted on the non-aromatic carbon atoms. By halogenating the carbon atoms other than the aromatic carbon atoms in accordance with the present invention, it is believed that: the alkyl constituents of the duroquinone. in them- .5 Claims; (01. 167-,30')

selves play a part in the toxicity of the compound 7 It is contemplated that'thehalogenated :duro

quinone containing an average of more than 50% by Weight of halogen may be used astsuch as a fungicide and parasiticidal material or itimay be used in suitable dispersion materials; For example, it may be used in the powder form as such and dusted on the surfaces where the insects and fungi may be encountered or it may be dis-- persed in finely divided materials such as'talc, clay, chalk and the like and dustedv on the infested areas. For example, it may be desired to dust animal life Which has been infested with insects with a, composition comprising halogenated duroquinone containing. an averagexofi more than 50% by weight of halogen substitutedfon the non-aromatic carbon atoms.

The improved insecticide and fungicide may also be used in fluid suspensions; For-exam le, the halogenated duroquinone having the properties listed above may be dissolved in'a hydrocarbon having solvent. properties for' the halogenated duroquinone. Such solvents include .white oil having a SSUviscosity at F. and other hydrocarbons as exemplified by light naphthas boiling as low asF.,'aromatic concentrates boiling no higher than about 285 F.,'low aromatic contentkerosenesboiling up to 425 F., and the like, including components thereof such as benzene, toluene, and the xylenes. V i

The halogenated duroquinone dissolved in a suitable solvent of the type mentioned before may thenbedispersed in water. When dispersing the halogenated duroquinone in water a Wetting' agent such as alkyl aryl sulfonate of an aromatic sulfonic acid, an alkali metal salt of a petroleum salt sulfonic acid and other dispersing agents such as exemplified by sulfonated lauryl alcohol, Turkey red oil and fish oil soaps, may be used;

The duroquinone, employed to prepare the halogenated derivative of the present invention, may suitably be prepared by the method's'de scribed in Organic Synthesis, v01. 10, H. T. Clark, Editor in Chief, John Wiley '&"Sons, Incl",

New York, 1940, pages40-42 inclusive. 'Dur'ene, derived from petroleum may be converted into duroquinone by careful nitration as outlined in the foregoing reference to produce-'a dinitrate derivative. The nitration may be accomplished by the action of the theoretical quantity of concentrated nitric acid in the presence'of concentrated sulfuric acid. The dinitrate derivative produced in this manner is then reduced to the amine. This reduction may be accomplished by the action of an acid on a metal such as iron or tin in the presence of the aromatic nitrate, The

oxidize this tin salt with ferric chloride in concentrated hydrochloric acid to produce duroquinone.

This halogenation may readily be accomplished by contacting the duroquinone in the presence, of light and/or a halogen carrier. This-method of halogenation is well known, and it is simple to control the halogenation to any desired degree such that it will contain an average of more than 50% by weight of halogen substituted on the nonaromatic carbon atoms.

While any halogen such as bromine, iodine or' chlorine may be employed, it is preferred to employ chlorine as the halogenating agent. Bromine maybe substituted for the .chlorine and. iodine may be employed, but it would be less desirable to use it foreconcmical reasons than'the other two. The conditions employed in the-halogenation may be used to produce halogenated duroquinone having an average of more than 50% by weight of halogen substituted on the non-aromatic carbon atom; A large number of compounds may thus be produced satisfying this'requirement. For instance, there are three hydrogens on each of the four methyl groups in duroquinone which are susceptible to replacement by halogen. It will be seenithat one hydrogen on each carbon atom may be'substituted or more than one may be substituted or two or more hydrogens may be substitutedon one of the methyl groups while other .of the methyl groups may. not be substituted at -all.'-The essential requirementof the present invention is that the halogenated duroquinone contain 'on'an average of more than 50% by Weight of halogen substituted on the non-aromatic carbon-atoms. By virtue of the halogen being substituted on the non-aromatic carbonatoms the degree of toxicity is not increased to an extent where the compound would be dangerous to higher forms of animal life such as represented by the vertebrate and mammalian forms. Thus the improved insecticide and fungicidemay be used on animals and in ridding crops of destructive'fungi. :In order to illustrate the invention further, chloroduroquinone was prepared which contained approximately-54.5% by weight of chlorine. This compound was formed into a suspension and was tested to determine its fungicidal properties to Alternaria solam' and Sclerotim'a fructzola. These fungi are the cause of early blight on potatoes and tomatoes and the appearance of brown rot on peaches, respectively. The testmethod employed has been-described by Horsfall, Fungicides and Their Action, The Chronica Botanica (30., Waltham, Massachusetts, 1945, in which the amount of fungicides necessary to obtain 50% morality is determined. I

In the particular technique employed, a culture of the common test organisms was maintained in the laboratory under sterile conditions. The slide germination method, which is Widely used in botanicalinvestigations, was employed asthe test method, In this technique fungus spores obtained under controlled conditions as regards species, strains, medium, age, temperature and concentration and stimulant, if desired, are suspended in distilled water. Aliquots of this suspension are pipetted into dilutions or suspensions .of ..the

chemical to be tested. Droplets of the resulting mixture are pipetted onto 1 by 3 inch glass slides. These are placed in moist chambers which are sealed with water and held at a temperature suitable for germination. After 20 hours the slides are removed from the moist chambers and the droplets examined under a low power microscope.

I The percentage spores inhibited from germinating, based on one hundred spores counted from a single compound, it is usually desirable to make several thousand spore counts.

It was found on testing fungicidal properties of the present invention that a solution in the range of 0.001 to 0.0001 weight per cent of the chlorinated duroquinone containing 54.5% by weight of chlorine allowed only 50% germination to Alternaria solam'. A similar test was carried out on Sclerotinia fructiola. These results show that the chlorinated duroquinone of the present invention has improved fungicidal properties.

The improved fungicide and insecticide of the present invention was then tested onmilk weed bug by immersinga specimen of the bug for'two minutes in a 0.25 weight per cent suspension of the improved fungicide and insecticide. A mortality to the'milk weed bug of 100% was obtained Similar tests with a suspension of the same concentration were performed on specimen of the German roach. In this test a morality of 30% was obtained.

The toxicity of the present invention wasthen tested on the American reach by injecting into the blood stream of male and female specimens 0.5 milligram of the compound per gram of body weight. This blood stream injection resulted in a mortality of 100 in both instances.

A suspension of the chlorinated duroquinone mentioned before having a chlorine content of approximately 54.5% by weight was employed in the housefly. The Nelson drop test showed mortality. The Nelson drop test is carried out by placing a measured droplet of a suspension or solution of the chemical of the present invention onto the ventral surface of the insects thorax. The treated insects are kept in holding cages'for four days and counts are made daily. The number of insects killed is employed in computing the efiicacy of the test. From these data it may be concluded that a suspension of the improved fungicide and insecticide of the present invention giay be employed to rid infested areas of house ies.

The toxicity of the compounds of the present invention was also tested on coleus to determine whether or not there was danger of plant life being harmed when used to combat fungi on vegetation. In every instance it was found that coleus suffered no injury when subjected to the improved fungicide and insecticide of the present invention.

It is indeed unusual that the chlorinated duro-' quinone containing 54.5% chlorine should be so efiective against milk weed bug, the female and male American roach, the house fly and against the two aforementioned fungi since an allied compound, tetrachlorobenzoquinone, did not show anywhere near the cf"- fectiveness when tested against the German roach or milk weed bug or American female and male roach. Not only is the tetrachlorobenzoquinone less effective than the chlorinated duroquinon'e, but duroquinone itself is not as effective as the chloroduroquinone. For example, the milk weed bug, where mortality was obtained with approximately of chloroduroquinone, only 15% mortality was effected with duroquinone. Likewise, where 160% mortality was obtained with chloroduroquinone against the female and male roach, only 80% mortality was efiected with duroquinone. It will be seen then that substituents on the methyl carbon atoms effect a marked superiority in toxicity to lower forms of animal life.

The reason why the halogenated duroquinone of the present invention is markedly superior to both tetrachlorobenzoquinone and duroquinone is not understood but it is postulated that the methyl groups with substituted halogens thereon contribute to the activational efiect conferred by the halogen to the compounds of the present invention. It is to be understood, however, that I do not bind myself by this postulate which is offered by way of explanation and not by way of limitation.

The nature and objects of the present invention having been completely described and illustrated, what I wish to claim as new and useful and to secure by Letters Patent is:

1. A fungicide and insecticide which comprises a chlorinated duroquinone containing approximately 54.5% by weight of chlorine substituted on the non-aromatic carbon atoms, a hydrocarbon, a wetting agent, and water.

2. A fungicide in accordance with claim 1 in which the hydrocarbon boils below 425 F.

3. A fungicide and insecticide which comprises a chlorinated duroquinone containing approximately 54.5% by weight of chlorine substituted on the non-aromatic carbon atoms and a finely divided solid dispersing agent.

4. A fungicide and insecticide which comprises a. chlorinated duroquinone containing approximately 54.5% by weight of chlorine substituted on the non-aromatic carbon atoms dissolved in a hydrocarbon in the amount and range between 1 and 10% by weight, said solution being dispersed in water containing a wetting agent in an amount in the range between 0.1 and 1% by weight of the water.

5. A fungicide and insecticide which comprises a chlorinated duroquinone containing approximately 54.5% by weight of chlorine substituted on the non-aromatic carbon atoms and a dispersing agent for the chlorinated duroquinone.

ALBERT J. SHMID-L.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Euler et a1. Chemical Abstracts, volume 39, pages 3786, 3787 (1945). 

1. A FUNGICIDE AND INSECTICIDE WHIC COMPRISES A CHLORINATED DUROQUINONE CONTAINING APPROXIMATELY 54.5% BY WEIGHT OF CHLORINE SUBSTITUTED ON THE NON-AROMATIC CARBON ATOMS, A HYDROCARBON, A WETTING AGENT, AND WATER. 